Photochromic compound, photochromic curable composition, cured product, lens, and eyeglasses

Abstract

The purpose of the present invention is to provide a photochromic compound which can exhibit photochromic characteristics regardless of a matrix, and is stably dispersed and present without being aggregated in an optical substrate forming process (during curing).　According to the present invention, a polymer photochromic compound, which has a group having a shape of a block polymer of an oligomer chain group having relatively excellent compatibility with a solid matrix and an oligomer chain group having poor compatibility with a solid matrix, forms a nano- to micro-phase separation structure in a solid matrix, improves dispersibility regardless of a solid matrix, and suppresses aggregation. As a result, a high level of photochromic characteristics can be exhibited.

Description

[Technical Field]

[0001] The present invention relates to a photochromic compound, a photochromic curable composition, a cured product, a lens, and eyeglasses. [Background technology]

[0002] Photochromic compounds, such as chromene compounds, fulgide compounds, and spirooxazine compounds, have the property (photochromicity) of rapidly changing color when irradiated with ultraviolet light such as sunlight or light from a mercury lamp, and returning to their original color when the light irradiation is stopped and they are placed in a dark place. Taking advantage of this property, they are used in a variety of applications, particularly as optical materials.

[0003] For example, eyeglass lenses containing a photochromic compound quickly become tinted outdoors when exposed to light containing ultraviolet light, such as sunlight, and function as sunglasses, whereas they fade indoors when not exposed to such light and function as transparent eyeglasses. Demand for photochromic optical articles with such photochromic properties has been increasing in recent years.

[0004] Examples of methods for producing such photochromic optical articles include methods using a photochromic composition containing a polymerizable compound and a photochromic compound. (a) A method in which a photochromic compound is dissolved in a polymerizable compound, which is then polymerized to form a hardened product, which is then directly used to make an optical article such as a lens. This method is called the kneading method. (b) A method in which a layer of a hardened material containing a dispersed photochromic compound is applied to the surface of a plastic molded product such as a lens by coating or cast polymerization. This method is called the lamination method. (c) A method in which two optical sheets are bonded together by curing an adhesive layer formed from an adhesive resin in which a photochromic compound has been dispersed. This method is called the binder method.

[0005] Optical articles to which photochromic properties have been imparted are further required to have the following properties: (I) The degree of coloring (initial coloring) in the visible light region before irradiation with ultraviolet light is low. (II) The coloring degree (color density) is high when irradiated with ultraviolet light. (III) The speed at which the color returns to its original state after the UV irradiation is stopped (fading speed) is fast. (IV) The reversible color-developing and fading action is durable. (V) High storage stability. (VI) It can be easily molded into various shapes.

[0006] Various photochromic compounds have been reported to date. However, it has been reported that even photochromic compounds that exhibit good photoresponsiveness in a liquid matrix tend to exhibit poor photoresponsiveness in a solid matrix and exhibit a long fading half-life. This is thought to be due to the fact that the free space in a solid matrix is ​​significantly smaller than in a liquid matrix, restricting the structural changes of the photochromic compound. To solve this problem, photochromic compounds containing oligomer chain groups such as polyalkyleneoxy oligomer chain groups or polysiloxane oligomer chain groups (hereinafter also referred to as "polymeric photochromic compounds") have been disclosed. These polymeric photochromic compounds have been reported to exhibit low matrix dependency and excellent photoresponsiveness even in a solid matrix because the oligomer chain groups can form free space. (See Patent Documents 1 to 6.) [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2004 / 041961 Brochure [Patent Document 2] International Publication No. 2000 / 015630 Brochure [Patent Document 3] International Publication No. 2009 / 146509 Brochure [Patent Document 4] International Publication No. 2012 / 149599 Brochure [Patent Document 5] International Publication No. 2012 / 162725 Brochure [Patent Document 6] Patent Publication No. 2019-182866 Summary of the Invention [Problem to be solved by the invention]

[0008] As described above, a polymeric photochromic compound exhibits high photochromic properties in a solid matrix. However, a cured product of a photochromic composition containing a polymeric photochromic compound may become cloudy. That is, if the compatibility between the solid matrix and the polymeric photochromic compound is low, the polymeric photochromic compound may aggregate in the cured product, causing cloudiness.

[0009] On the other hand, low molecular weight photochromic compounds that do not have an oligomer chain group do not aggregate in a solid matrix, and therefore, when a composition containing only a low molecular weight photochromic compound is used, a transparent photochromic cured product can be obtained. However, low molecular weight photochromic compounds are highly matrix-dependent, and in some cases, the fading speed and other aspects of the photochromic property can become a problem in a solid matrix.

[0010] An object of the present invention is to provide a photochromic compound that can exhibit photochromic properties independently of a matrix and that exists in a cured product stably dispersed without agglomeration, as well as a photochromic curable composition, a cured product, a lens, and eyeglasses that contain this photochromic compound. [Means for solving the problem]

[0011] In order to solve the above problems, the present inventors have studied the compatibility between a polymeric photochromic compound and a solid matrix while ensuring free space, and have concluded that the compatibility with the solid matrix can be improved while ensuring free space by doing the following.

[0012]

[0009] Specifically, the present inventors considered that by using a polymeric photochromic compound having a block polymer group composed of an oligomer chain group having relatively good compatibility with the solid matrix and an oligomer chain group having poor compatibility with the solid matrix, the oligomer chain group portion having good compatibility with the solid matrix will be compatible with the solid matrix, while the oligomer chain group portion having poor compatibility will form free space, forming a nano- to micro-phase-separated structure, and as a result, the polymeric photochromic compound will not aggregate in the solid matrix and will have improved dispersibility. Therefore, the present inventors investigated various block polymer groups as the oligomer chain group and found that when a specific combination of block polymer groups is used, the polymeric photochromic compound can exhibit high photochromic properties while having good dispersibility in the solid matrix, thereby completing the present invention.

[0013] That is, the first embodiment is The photochromic compound is represented by the following formula (1) or (2). [ka] [ka] (In the formula, PC is a group having at least one photochromic moiety. In the case of the photochromic compound represented by the formula (1), a combination in which X1 is a polyoxypropylene group having 3 to 200 repeating units and X2 is a polyoxyethylene group having 3 to 200 repeating units; a combination in which X1 is a polyoxyethylene group having 3 to 200 repeating units and X2 is a polyoxypropylene group having 3 to 200 repeating units; a combination of X1 being a polyoxytetramethylene group having 3 to 200 repeating units and X2 being any one of a polyoxyethylene group having 3 to 200 repeating units, a polyoxypropylene group having 3 to 200 repeating units, and a polysiloxane group having 3 to 200 repeating units and having a linear alkyl group having 1 to 10 carbon atoms as a substituent; X1 is a polysiloxane group having 3 to 200 repeating units and having a linear alkyl group having 1 to 10 carbon atoms as a substituent, and X2 is a combination of a polyoxyethylene group having 3 to 200 repeating units or a polyoxypropylene group having 3 to 200 repeating units, In the case of the photochromic compound represented by the formula (2), A combination of X1 being a polyoxypropylene group having 3 to 200 repeating units, X2 being a linear alkylene group having 12 to 30 carbon atoms, and X3 being a polyoxyethylene group having 3 to 200 repeating units. Z is 、 It is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms. L1 is 、 It is a divalent bond. L2 is 、 It is an m+1 valent bond. L3 is 、 It is an l+1-valent bond. n is an integer of 1 to 8. m is an integer of 1 to 4. l is an integer of 1 to 4.

[0014] The second embodiment is a photochromic curable composition containing the photochromic compound according to the embodiment and a polymerizable compound.

[0015] The third embodiment is a cured product obtained by polymerizing the photochromic curable composition according to the embodiment. The fourth embodiment is a lens including a cured body according to an embodiment. A fifth embodiment is a pair of glasses including a lens according to an embodiment. [Effects of the Invention]

[0016] The photochromic compound of the present invention exhibits excellent photochromic properties in a solid matrix. Furthermore, when existing polymeric photochromic compounds are used, problems such as cloudiness of the cured product may occur, but when the photochromic compound of the present invention is used, a transparent photochromic cured product having good photochromic properties can be produced. DETAILED DESCRIPTION OF THE INVENTION

[0017] According to an embodiment, there is provided a photochromic compound represented by the following formula (1): [ka] In formula (1), PC is a group having at least one photochromic moiety. X1 is an alkylene group, a polyoxypropylene group, a polyoxyethylene group, a polyoxytetramethylene group, or a polysiloxane group. X2 is an alkylene group, a polyoxypropylene group, a polyoxyethylene group, or a polyoxytetramethylene group. X1 and X2 are different groups. When X2 is an alkylene group, Z is a hydrogen atom, a methyl group, or an alkyloxy group having 1 to 10 carbon atoms. When X2 is a polyoxypropylene group, a polyoxyethylene group, a polyoxytetramethylene group, or a polysiloxane group, Z is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms. L1 is a direct or divalent bond. L2 is a direct bond or an m+1 valent bond. n is an integer of 1 to 8. m is an integer of 1 to 4. According to an embodiment, there is also provided a photochromic compound represented by the following formula (2): [ka] In formula (2), PC, X1, X2, L1, L2, m, and n have the same meanings as in formula (1). X3 is an alkylene group, a polyoxypropylene group, a polyoxyethylene group, a polyoxytetramethylene group, or a polysiloxane group. X1 and X2 are different groups. X2 and X3 are different groups. X1 and X3 may be the same group or different groups. When X3 is an alkylene group, Z is a hydrogen atom, a methyl group, or an alkyloxy group having 1 to 10 carbon atoms. When X3 is a polyoxypropylene group, a polyoxyethylene group, a polyoxytetramethylene group, or a polysiloxane group, Z is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms. L3 is a direct bond or a l+1-valent bond. l is an integer of 1 to 4. In X1, X2, or X3, the number of carbon atoms in the alkylene group is preferably 12 to 30, and more preferably 12 to 20. The alkylene group may be linear or branched, but is preferably linear. In X1, X2, or X3, the repeating unit of the polyoxypropylene group is represented by (—CH2-CH(CH3)—O—). The number of repeating units is 3 to 200, preferably 5 to 150, more preferably 5 to 100, and even more preferably 10 to 50. In X1, X2, or X3, the repeating unit of the polyoxyethylene group is represented by (—CH2—CH2—O—). The number of repeating units is 3 to 200, preferably 5 to 150, more preferably 5 to 100, and even more preferably 10 to 50. In X1, X2, or X3, the repeating unit of the polyoxytetramethylene group is represented by (—CH2—CH2—CH2—CH2—O—). The number of repeating units is 3 to 200, preferably 5 to 150, more preferably 5 to 100, and even more preferably 10 to 50. In X1, X2, or X3, the repeating unit of the polysiloxane group is (—Si(R 10 )2-O-) is a silyleneoxy group (siloxane group). 10 R is a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyloxy group having 1 to 10 carbon atoms, or an aromatic group having 6 to 10 carbon atoms. 10 is preferably an alkyl group, more preferably a methyl group. 10 may be different from each other or may be the same, but are preferably the same. The number of repeating units of the polysiloxane group is 3 to 200, preferably 5 to 150, more preferably 5 to 100, and even more preferably 10 to 50. The photochromic compound according to the embodiment includes oligomer chains X1 and X2 having different structures. It is believed that the compatibility of X1 and X2 in a specific matrix differs. X1 exhibiting relatively high compatibility in a specific matrix can contribute to the photochromic compound being less likely to aggregate. X2 exhibiting relatively low compatibility can contribute to the formation of free space in the matrix where the photochromic compound is more likely to undergo structural changes. In other matrices, X1 may exhibit relatively low compatibility, while X2 may exhibit relatively high compatibility. Therefore, when a composition containing a photochromic compound having both X1 and X2 is used, a cured product with excellent photochromic properties and high transparency can be obtained, regardless of the type of matrix. Furthermore, in the photochromic compound according to the embodiment, Z is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms. When the compound has these structures, the microlayer-separated structure can be formed more effectively. Furthermore, the photochromic compound according to the embodiment may contain a linking group L2 between X1 and X2. In the photochromic compound containing the linking group L2 between X1 and X2, the linking group L1 allows the portions with different compatibility to be clearly separated, so that the microphase-separated structure can be formed more effectively.

[0018] This will be explained in detail below. <X1、X2、X3> X1 and X3 in the photochromic compound are each independently an oligomer chain group selected from a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxypropylene group having 3 to 200 repeating units, a polyoxyethylene group having 3 to 200 repeating units, a polyoxytetramethylene group having 3 to 200 repeating units, or a polysiloxane group having 3 to 200 repeating units and consisting of a silyleneoxy group having two substituents selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms.

[0019] X2 is an oligomer chain group selected from a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxypropylene group having 3 to 200 repeating units, a polyoxyethylene group having 3 to 200 repeating units, or a polyoxytetramethylene group having 3 to 200 repeating units.

[0020] As the linear or branched alkylene group having 12 to 30 carbon atoms, a linear alkylene group is preferred.

[0021] Furthermore, as the polysiloxane group consisting of a silyleneoxy group having two substituents selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms, a polydimethylsiloxane group, or a polymethylphenylsiloxane group is preferred.

[0022] In the photochromic compound, X1 and X2, which are bonded via the bond L2 described below, and / or X2 and X3, which are bonded via the bond L3, are selected from different groups. However, X1 and X3 may be the same group or different groups. In this way, by making X1 and X2, and X2 and X3 different groups, a block polymer-like group is formed, and it is believed that the effects of the present invention can be achieved.

[0023] For example, when X2 is a polyoxypropylene group having 3 to 200 repeating units, X1 and X3 are groups other than polyoxypropylene groups having 3 to 200 repeating units, i.e., oligomer chain groups selected from linear or branched alkylene groups having 12 to 30 carbon atoms, polyoxyethylene groups having 3 to 200 repeating units, polyoxytetramethylene groups having 3 to 200 repeating units, or polysiloxane groups having 3 to 200 repeating units and consisting of silyleneoxy groups having two substituents selected from linear or branched alkyl groups having 1 to 10 carbon atoms, linear or branched alkoxy groups having 1 to 10 carbon atoms, and aromatic groups having 6 to 10 carbon atoms.

[0024] The combination of X1, X2, and X3 may be appropriately determined depending on the desired photochromic performance and the type of solid matrix in which the photochromic compound is dispersed.

[0025] Among these, in the case of the photochromic compound represented by the formula (1), a combination in which X1 is an oligomer chain group selected from a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxypropylene group having 3 to 200 repeating units, or a polysiloxane group having 3 to 200 repeating units and consisting of a silyleneoxy group having two substituents selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms, and X2 is an oligomer chain group selected from a polyoxyethylene group having 3 to 200 repeating units or a polyoxytetramethylene group having 3 to 200 repeating units; a combination in which X1 is a polyoxyethylene group having 3 to 200 repeating units, and X2 is an oligomer chain group selected from a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxypropylene group having 3 to 200 repeating units, or a polyoxytetramethylene group having 3 to 200 repeating units; or a combination in which X1 is a polyoxytetramethylene group having 3 to 200 repeating units, and X2 is an oligomer chain group selected from a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxypropylene group having 3 to 200 repeating units, or a polyoxyethylene group having 3 to 200 repeating units; is preferred.

[0026] In the case of the photochromic compound represented by the formula (2), X1 is a polyoxyethylene group having 3 to 200 repeating units, X2 is an oligomer chain group selected from a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxypropylene group having 3 to 200 repeating units, or a polyoxytetramethylene group having 3 to 200 repeating units, and X3 is a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxyethylene group having 3 to 200 repeating units, or a polyoxytetramethylene group having 3 to 200 repeating units. an oligomer chain group selected from a polyoxypropylene group, a polyoxytetramethylene group having 3 to 200 repeating units, or a polysiloxane group having 3 to 200 repeating units and consisting of a silyleneoxy group having two substituents selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms, wherein X2 and X3 are different combinations; X1 is an oligomer chain group selected from a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxypropylene group having 3 to 200 repeating units, or a polysiloxane group having 3 to 200 repeating units and consisting of a silyleneoxy group having two substituents selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms; and X2 is an oligomer chain group selected from a polyoxyethylene group having 3 to 200 repeating units or a polyoxytetramethylene group having 3 to 200 repeating units. X3 is an oligomer chain group selected from a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxyethylene group having 3 to 200 repeating units, a polyoxypropylene group having 3 to 200 repeating units, a polyoxytetramethylene group having 3 to 200 repeating units, or a polysiloxane group having 3 to 200 repeating units and consisting of a silyleneoxy group having two substituents selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms, and X2 and X3 are different combinations; or X1 is a polyoxytetramethylene group having 3 to 200 repeating units, X2 is an oligomer chain group selected from a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxyethylene group having 3 to 200 repeating units, or a polyoxypropylene group having 3 to 200 repeating units, and X3 is a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxyethylene group having 3 to 200 repeating units, or a polyoxypropylene group having 3 to 200 repeating units. an oligomer chain group selected from a polyoxypropylene group, a polyoxytetramethylene group having 3 to 200 repeating units, or a polysiloxane group having 3 to 200 repeating units and consisting of a silyleneoxy group having two substituents selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms, wherein X2 and X3 are different combinations; is preferred.

[0027] The X1, X2, and X3 are not particularly limited, but are significantly affected by the structure of the solid matrix, and may be appropriately selected in consideration of compatibility with the solid matrix.

[0028] For example, in the case of a thiourethane- or urethane-based solid matrix, it is preferable that the oligomer chain group having excellent compatibility is selected from a polyoxymethylene group having 3 to 200 repeating units or a polyoxytetramethylene group having 3 to 200 repeating units, and the oligomer chain group having poor compatibility is selected from a linear or branched alkylene group having 12 to 30 carbon atoms, a polyoxypropylene group having 3 to 200 repeating units, or a polysiloxane group having 3 to 200 repeating units and consisting of a silyleneoxy group having two substituents selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms, and that these oligomer chain groups be combined to form a block polymer group.

[0029] In the case of an acrylic solid matrix, it is preferable that the oligomer chain group having excellent compatibility is selected from a polyoxymethylene group having 3 to 200 repeating units or a polyoxytetramethylene group having 3 to 200 repeating units, and the oligomer chain group having poor compatibility is selected from a polyoxypropylene group having 3 to 200 repeating units or a polysiloxane group having 3 to 200 repeating units and consisting of a silyleneoxy group having two substituents selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms, and that these oligomer chain groups be combined to form a block polymer group.

[0030] The number of repeating units of the polyoxypropylene group having 3 to 200 repeating units, the polyoxymethylene group having 3 to 200 repeating units, the polyoxytetramethylene group having 3 to 200 repeating units, or the polysiloxane group having 3 to 200 repeating units and consisting of a silyleneoxy group having two substituents selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms is more preferably 4 to 150, even more preferably 5 to 120, and most preferably 6 to 100.

[0031] In the formulas (1) and (2), the number-average molecular weight of the portion excluding the photochromic moiety-containing group PC is not particularly limited as long as it is within the range of the number of repeating units described above. However, it is preferably 300 to 20,000, more preferably 400 to 15,000, even more preferably 500 to 12,000, and most preferably 600 to 10,000 per group having a photochromic moiety. By setting the number-average molecular weight at or above the lower limit, a nano- to micro-phase-separated structure is formed, sufficient free space is formed in the solid matrix, and photochromic properties tend to be improved. Furthermore, by setting the number-average molecular weight at or below the upper limit, the concentration of the photochromic compound per unit weight does not decrease, and there is no need to add more than necessary. <pc> The photochromic compound must have a group PC having at least one photochromic moiety in the molecule. Any known photochromic moiety can be used.

[0032] Furthermore, the photochromic compound is not particularly limited as long as it has at least one group having a photochromic moiety. In particular, taking into consideration the productivity and photochromic properties of the photochromic compound itself, the number of groups having a photochromic moiety is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 to 2. When a photochromic compound has a plurality of groups having a photochromic moiety, these may each be a photochromic moiety with the same structure, or two or more different photochromic moieties.

[0033] Representative examples of such photochromic moieties include naphthopyran, spirooxazine, spiropyran, fulgide, fulgimide, and diarylethene.

[0034] Among these, naphthopyran, spirooxazine, and spiropyran are preferred, naphthopyran is more preferred, and indenonaphthopyran is even more preferred, from the viewpoint of being able to exhibit excellent photochromic properties, particularly in terms of color density and fading speed, and among these, indeno[2,1-f]naphtho[1,2-b]pyran is particularly preferred.

[0035] Indeno[2,1-f]naphtho[1,2-b]pyran, which is a particularly preferred example of the photochromic moiety, is represented by the following formula (6):

[0036] [ka]

[0037] (In the formula, R 1 and R 2 each independently represents a group bonded to L1 described below, or a hydroxyl group, an alkyl group, a haloalkyl group, an optionally substituted cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, an amido group, a substituted amido group, an optionally substituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group, an optionally substituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an optionally substituted aralkyl group, an optionally substituted aralkoxy group, an optionally substituted aryloxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or an optionally substituted cycloalkylthio group, a is an integer from 0 to 4, and b is an integer from 0 to 4, When a is 2 to 4, multiple R 2 may be the same or different from each other, When b is 2 to 4, multiple R 1 may be the same or different from each other, In addition, a is 2 to 4, and adjacent R 2 If there is a 2 Together they R 2 may form a ring together with the carbon atom bonded to it which may contain an oxygen atom, a carbon atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent; In addition, b is 2 to 4, and adjacent R 1 If there is a 1 Together they R 1 may form a ring together with the carbon atom bonded to it which may contain an oxygen atom, a carbon atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent; R 3 and R 4 each independently represents an aryl group or a heteroaryl group which may be substituted with a substituent, and the substituent is a group which may be bonded to L1; R 5 and R 6 each independently represents a group bonded to L1 described below, or a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; Also, R 5 and R 6 may combine together with the carbon atom at position 13 to which they are bonded to form an aliphatic ring having 3 to 20 ring carbon atoms, a condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the aliphatic ring, a heterocycle having 3 to 20 ring atoms, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle, provided that these rings may have a substituent, However, R 1 , R 2 , R 3 a substituent on the aryl or heteroaryl group of 4 a substituent on the aryl or heteroaryl group of 5 and R 6 At least one selected from the following is a group that bonds to L1 described below.

[0038] Furthermore, with regard to each of the groups exemplified above, the alkyl group preferably has 1 to 10 carbon atoms, the haloalkyl group preferably has 1 to 10 carbon atoms, the cycloalkyl group preferably has 3 to 8 carbon atoms, the alkoxy group preferably has 1 to 10 carbon atoms, the alkylcarbonyl group preferably has 2 to 7 carbon atoms, the alkoxycarbonyl group preferably has 2 to 7 carbon atoms, the aralkyl group preferably has 7 to 11 carbon atoms, the aralkoxy group preferably has 7 to 11 carbon atoms, the aryloxy group preferably has 6 to 12 carbon atoms, the aryl group preferably has 6 to 12 carbon atoms, the alkylthio group preferably has 1 to 10 carbon atoms, the cycloalkylthio group preferably has 3 to 8 carbon atoms, and the arylthio group preferably has 6 to 12 carbon atoms.

[0039] R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In the above, the substituents that may be contained in these groups or in the ring groups formed by these groups are introduced mainly to control the color tone and the like, and it goes without saying that the effects are not impaired by these substituents.

[0040] Among these, the following groups are preferred in order to exhibit excellent photochromic properties.

[0041] R 1 is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted amino group, a heterocyclic group which may have a substituent, an alkylthio group, an arylthio group which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent. Among these, it is more preferable that these groups are present at the 6th and / or 7th positions of the indeno[2,1-f]naphtho[1,2-b]pyran. In addition, when R is present at the 6th and 7th positions, 1 are also preferably present and together form an aliphatic ring (which may further have a substituent) which may contain an oxygen atom, a nitrogen atom, or a sulfur atom. In this case, the number of atoms in the aliphatic ring containing the oxygen atom, nitrogen atom, or sulfur atom (the number of atoms including heteroatoms and the carbon atoms located at the 6th and 7th positions) is preferably 5 to 8. Furthermore, the aliphatic ring may have a substituent, and this substituent is preferably an alkyl group having 1 to 6 carbon atoms.

[0042] R 2 is preferably a hydrogen atom (when a=0), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted amino group, a heterocyclic group which may have a substituent, a haloalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a cyano group, or an arylthio group. Of these, it is more preferable that these groups are present at the 11-position of indeno[2,1-f]naphtho[1,2-b]pyran.

[0043] R 3 , and R 4 is preferably an aryl group having 6 to 12 ring carbon atoms. Preferred substituents on the aryl group include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted amino group, a heterocyclic group having a ring nitrogen atom and bonded to the carbon atom to which it is bonded via the nitrogen atom (which may have a substituent), and an arylthio group which may have a substituent. It is particularly preferred that at least one of the substituents is a bond L1 described in detail below.

[0044] R 5 , and R 6 More preferably, R is an alkyl group having 1 to 10 carbon atoms or L1, which will be described in detail below. 5 and R 6 More preferably, two of these groups, together with the carbon atom at position 13 to which they are bonded, form an aliphatic ring having 3 to 20 ring carbon atoms, a fused polycyclic ring in which an aromatic ring or a heteroaromatic ring is fused to the aliphatic ring, a heterocyclic ring having 3 to 20 ring atoms, or a fused polycyclic ring in which an aromatic ring or a heteroaromatic ring is fused to the heterocyclic ring. Among these, a ring selected from a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, and a spirodicyclohexane ring is particularly preferred. The spiro ring may have 1 to 10 alkyl groups having 1 to 6 carbon atoms or cycloalkyl groups having 5 to 7 carbon atoms as substituents, or may be fused to cycloalkyl groups having 5 to 7 carbon atoms. Examples of more suitable groups include groups represented by the following formulas:

[0045] [ka]

[0046] Indeno[2,1-f]naphtho[1,2-b]pyrans that form the above-described photochromic moieties are disclosed, for example, in International Publication Nos. 1996 / 014596, 2001 / 019813, 2001 / 060811, 2005 / 028465, 2006 / 110221, 2007 / 073462, 2007 / 140071, and 2008 / 054942. Compounds described in WO 2010 / 065393, WO 2011 / 10744, WO 2011 / 016582, WO 2011 / 025056, WO 2011 / 034202, WO 2011 / 078030, WO 2012 / 102409, WO 2012 / 102410, WO 2012 / 121414, and the like can be used without any restrictions.

[0047] The group that binds to L1 is R 1 , R 2 , R 3 a substituent on the aryl or heteroaryl group of 4 a substituent on the aryl or heteroaryl group of 5 and R 6 In the group described in , it may be a substituent possessed by a group that may have a substituent. In particular, the group bonded to L1 is preferably substituted at the 3-, 6-, 7-, 11-, or 13-position of the indenonaphthopyran. Among these, the 3- and 13-positions are particularly preferred, as this can improve the productivity of the photochromic compound itself. <z> When X2 in formula (1) or X3 in formula (2) is a linear or branched alkylene group having 12 to 30 carbon atoms, Z is a hydrogen atom, a methyl group, or an alkyloxy group having 1 to 10 carbon atoms. Z is preferably a methyl group. When X2 in formula (1) or X3 in formula (2) is a polyoxypropylene group having 3 to 200 repeating units, a polyoxyethylene group having 3 to 200 repeating units, a polyoxytetramethylene group having 3 to 200 repeating units, or a polysiloxane group having 3 to 200 repeating units and consisting of a silyleneoxy group having two substituents selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyloxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms, Z is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms. Z is preferably an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms. <l1> L1 is a divalent bond that directly bonds or bonds the photochromic moiety PC to the oligomer chain group X1.

[0048] Among them, the following formula (3)

[0049] [ka]

[0050] (In the formula, Y1 and Y2 are divalent groups, each independently a direct bond, -O-, -S-, an amino group, a substituted amino group, a carbonyl group, or a group formed by a combination thereof (an example of a combination is an ester group formed by combining -O- and a carbonyl group), or a substituted silylene group; A1 is a divalent group, which is directly bonded, or is an alkylene group having 1 to 10 carbon atoms which may have a substituent, a cycloalkylene group having 3 to 12 ring carbon atoms which may have a substituent, an arylene group having 6 to 12 ring carbon atoms which may have a substituent, or a heterocyclic group having 3 to 12 ring atoms which may have a substituent, o is an integer of 1 to 3, and p is an integer of 1 to 5; When o is 2 or more, the divalent groups of the multiple o units may be the same or different, When p is 2 or more, the divalent groups of the multiple p units may be the same or different. A group represented by the following formula is preferred.

[0051] Among these, particularly preferred groups are: A1 is preferably a direct bond, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclohexylene group, a phenylene group, or a group in which the methylene group of a cyclohexylene group has been substituted with NH.

[0052] Y1 and Y2 are each preferably a group selected from a direct bond, -O-, -S-, a carbonyl group, an ester group, a thioester group, an amide group, a urethane group, a thiourethane group, a dimethylsilylene group, and an amino group.

[0053] L1 is not particularly limited, but the following groups, which are direct bonds or combinations of the particularly preferred groups described above, are preferably used. (In the formula, the dashed line portion is the portion that binds to the photochromic moiety PC and X1.)

[0054] [ka] L1 is preferably a divalent bond represented by the following formula (3'). [ka] In formula (3'), V1, V2, V3, and V4 each independently represent an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a dimethylsilylene group, a dimethylsilyleneoxy group, a carbonyl group, a carbonyloxy group, an aminocarbonyloxy group, an aminooxycarbonyl group, an alkylene group having from 1 to 10 carbon atoms, an oxyalkylene group having from 1 to 10 carbon atoms, an oxyalkylene group having from 1 to 10 carbon atoms and having a hydroxy group as a substituent, a dioxyalkylene group having from 1 to 10 carbon atoms, a carbonylalkylene group having from 2 to 10 carbon atoms, a dicarbonylalkylene group having from 3 to 10 carbon atoms, an alkylene group having from 1 to 10 carbon atoms The alkylene group is a thioalkylene group, an aminoalkylene group having from 1 to 10 carbon atoms, an oxycarbonylalkylene group having from 2 to 10 carbon atoms, a carbonyloxyalkylene group having from 2 to 10 carbon atoms, an aminocarbonyloxyalkylene group having from 2 to 10 carbon atoms, a cycloalkylene group having from 3 to 10 carbon atoms, a cycloalkylenecarbonyl group having from 4 to 10 carbon atoms, a cycloalkyleneoxycarbonyl group having from 4 to 10 carbon atoms, a cycloalkylenecarbonyloxy group having from 4 to 10 carbon atoms, a heterocycloalkylene group having from 1 to 10 carbon atoms, or a heterocycloalkylenecarbonyl group having from 2 to 10 carbon atoms. α, β, γ, and δ are each 0 or 1. α+β+γ+δ is 1 or greater and 4 or less. The dashed bond extending from V4 bonds to X1. The solid bond extending from V1 bonds to PC.

[0055] <L2、L3> L2 is a bond having a valence of m+1 that directly bonds or bonds two different oligomer chain groups X1 and X2.

[0056] Among them, the following formula (4)

[0057] [ka]

[0058] (In the formula, Y3 and Y4 are divalent groups, each independently representing a direct bond, -O-, -S-, an amino group, a substituted amino group, a carbonyl group, or a group formed from a combination thereof, or a substituted silylene group; A2 is an m-valent group, which is a direct bond (only when m=1) or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms; q is an integer of 1 to 3, and r is an integer of 1 to 5; When q is 2 or more, the multiple q groups may be the same or different from each other, When r is 2 or more, the multiple r groups may be the same or different. A group represented by the following formula is preferred.

[0059] Among these, particularly preferred groups are: A2 is a direct bond, or a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, or a group represented by the following formula, which has a substituent selected from an alkoxyl group, a methyl group, an ethyl group, a propyl group, and a hydroxyl group as a substituent.

[0060] [ka]

[0061] (In the formula, the dashed line represents a bond to Y3 or Y4, and B represents a hydrogen atom or a substituent selected from a methyl group, an ethyl group, a propyl group, a hydroxyl group, and an alkoxyl group.) It is preferable that:

[0062] Y3 and Y4 are preferably a direct bond, -O-, -S-, a carbonyl group, an ester group, a thioester group, an amide group, a urethane group, a thiourethane group, a dimethylsilylene group, or an amino group. L3 is a (l+1)-valent bond that directly bonds or bonds two different oligomer chain groups X2 and X3.

[0063] Among them, the following formula (5)

[0064] [ka]

[0065] (In the formula, Y5 and Y6 are divalent groups, each independently representing a direct bond, -O-, -S-, an amino group, a substituted amino group, a carbonyl group, or a group formed from a combination thereof, or a substituted silylene group; A3 is a l-valent group, which is a direct bond (only when l=1) or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent; s is an integer from 1 to 3, and t is an integer from 1 to 5; When s is 2 or more, the multiple s groups may be the same or different, When t is 2 or more, the multiple t groups may be the same or different. A group represented by the following formula is preferred.

[0066] Among these, particularly preferred groups are: A3 is a direct bond, or a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, or a group represented by the following formula, which has a substituent selected from an alkoxyl group, a methyl group, an ethyl group, a propyl group, and a hydroxyl group as a substituent.

[0067] [ka]

[0068] (In the formula, the dashed line represents a bond to Y5 or Y6, and B represents a hydrogen atom or a substituent selected from a methyl group, an ethyl group, a propyl group, a hydroxyl group, and an alkoxyl group.) It is preferable that:

[0069] Y5 and Y6 are preferably a direct bond, -O-, -S-, a carbonyl group, an ester group, a thioester group, an amide group, a urethane group, a thiourethane group, a dimethylsilylene group, or an amino group.

[0070] L2 and L3 are not particularly limited, but when m and l are 1, the following groups, which are direct bonds or combinations of the particularly preferred groups described above, are preferably used. (In the formula, the dashed lines represent bonds to X1, X2, or X3.)

[0071] [ka]

[0072] When m and l are 2 or more, the following are preferably used. (In the formula, the dashed line represents a bond to X1, X2, or X3.)

[0073] [ka] L2 and L3 can each be a divalent bond represented by the following formula (4').

[0074] [ka] In formula (4'), V5, V6, V7, and V8 each independently represent an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a dimethylsilylene group, a dimethylsilyleneoxy group, a carbonyl group, a carbonyloxy group, an aminocarbonyloxy group, an aminooxycarbonyl group, an alkylene group having from 1 to 10 carbon atoms, an oxyalkylene group having from 1 to 10 carbon atoms, an oxyalkylene group having from 1 to 10 carbon atoms and having a hydroxy group as a substituent, a dioxyalkylene group having from 1 to 10 carbon atoms, a carbonylalkylene group having from 2 to 10 carbon atoms, a dicarbonylalkylene group having from 3 to 10 carbon atoms, an alkylene group having from 1 to 10 carbon atoms The alkylene group is a thioalkylene group, an aminoalkylene group having from 1 to 10 carbon atoms, an oxycarbonylalkylene group having from 2 to 10 carbon atoms, a carbonyloxyalkylene group having from 2 to 10 carbon atoms, an aminocarbonyloxyalkylene group having from 2 to 10 carbon atoms, a cycloalkylene group having from 3 to 10 carbon atoms, a cycloalkylenecarbonyl group having from 4 to 10 carbon atoms, a cycloalkyleneoxycarbonyl group having from 4 to 10 carbon atoms, a cycloalkylenecarbonyloxy group having from 4 to 10 carbon atoms, a heterocycloalkylene group having from 1 to 10 carbon atoms, or a heterocycloalkylenecarbonyl group having from 2 to 10 carbon atoms. ε, ζ, η, and θ are each 0 or 1. ε + ζ + η + θ is 1 or greater and 4 or less. In the case of L2, the dashed bond extending from V5 is bonded to X1, and the solid bond extending from V8 is bonded to X2. In the case of L3, the dashed bond extending from V5 is bonded to X2, and the solid bond extending from V8 is bonded to X3. L2 and L3 can each be a trivalent bond represented by the following formula (5').

[0075] [ka] In formula (5'), W1 is a trivalent group which is CH, CW8, or a nitrogen atom, and W8 is a linear or branched alkyl group having 1 to 10 carbon atoms. W2, W3, W4, W5, W6, and W7 each independently represent an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a dimethylsilylene group, a dimethylsilyleneoxy group, a carbonyl group, a carbonyloxy group, an aminocarbonyloxy group, an aminooxycarbonyl group, an alkylene group having from 1 to 10 carbon atoms, an oxyalkylene group having from 1 to 10 carbon atoms, an oxyalkylene group having from 1 to 10 carbon atoms and having a hydroxy group as a substituent, a dioxyalkylene group having from 1 to 10 carbon atoms, a carbonylalkylene group having from 2 to 10 carbon atoms, a dicarbonylalkylene group having from 3 to 10 carbon atoms, a thioalkylene group having from 1 to 10 carbon atoms, alkylene groups, aminoalkylene groups having from 1 to 10 carbon atoms, oxycarbonylalkylene groups having from 2 to 10 carbon atoms, carbonyloxyalkylene groups having from 2 to 10 carbon atoms, aminocarbonyloxyalkylene groups having from 2 to 10 carbon atoms, cycloalkylene groups having from 3 to 10 carbon atoms, cycloalkylenecarbonyl groups having from 4 to 10 carbon atoms, cycloalkyleneoxycarbonyl groups having from 4 to 10 carbon atoms, cycloalkylenecarbonyloxy groups having from 4 to 10 carbon atoms, heterocycloalkylene groups having from 1 to 10 carbon atoms, or heterocycloalkylenecarbonyl groups having from 2 to 10 carbon atoms. κ, λ, and v are each 0 or 1. In the case of L2, the dashed bond extending from W3 is bonded to X1, and the solid bonds extending from W5 and W7 are bonded to X2. In the case of L3, the dashed bond extending from W3 is bonded to X2, and the solid bonds extending from W5 and W7 are bonded to X3. L2 and L3 can each be a tetravalent bond represented by the following formula (6'). [ka] In formula (6'), U1, U2, U3, U4, U5, U6, U7, U8, and U9 each independently represent an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a dimethylsilylene group, a dimethylsilyleneoxy group, a carbonyl group, a carbonyloxy group, an aminocarbonyloxy group, an aminooxycarbonyl group, an alkylene group having from 1 to 10 carbon atoms, an oxyalkylene group having from 1 to 10 carbon atoms, an oxyalkylene group having from 1 to 10 carbon atoms and having a hydroxy group as a substituent, a dioxyalkylene group having from 1 to 10 carbon atoms, a carbonylalkylene group having from 2 to 10 carbon atoms, a dicarbonylalkylene group having from 3 to 10 carbon atoms, The alkylene group is a thioalkylene group having from 1 to 10 carbon atoms, an aminoalkylene group having from 1 to 10 carbon atoms, an oxycarbonylalkylene group having from 2 to 10 carbon atoms, a carbonyloxyalkylene group having from 2 to 10 carbon atoms, an aminocarbonyloxyalkylene group having from 2 to 10 carbon atoms, a cycloalkylene group having from 3 to 10 carbon atoms, a cycloalkylenecarbonyl group having from 4 to 10 carbon atoms, a cycloalkyleneoxycarbonyl group having from 4 to 10 carbon atoms, a cycloalkylenecarbonyloxy group having from 4 to 10 carbon atoms, a heterocycloalkylene group having from 1 to 10 carbon atoms, or a heterocycloalkylenecarbonyl group having from 2 to 10 carbon atoms. ξ, π, ρ, and σ are each 0 or 1. In the case of L2, the dashed bond extending from U3 is bonded to X1, and the solid bonds extending from U5, U7, and U9 are bonded to X2. In the case of L3, the dashed bond extending from U3 is bonded to X2, and the solid bonds extending from U5, U7, and U9 are bonded to X3.

[0076] <Specific examples of photochromic compounds> The photochromic compound is shown by the following formula and the compounds exemplified in the Examples, but these are merely examples and are not intended to be limiting.

[0077] In the formula, x, y, and z represent the number of repeating units and are selected from 3 to 200. Note that oligomer chain groups usually have multiple molecular weights, so they are expressed as number average molecular weights. Therefore, x, y, and z can take values ​​other than integers. Also, x, y, and z may be different values ​​or the same value. Note that "Me" in the formula means a methyl group.

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] <Method for producing photochromic compounds> The photochromic compound may be produced by any synthesis method. A representative example of a method for producing a photochromic compound will be described below, but the method is not limited to this.

[0086] For example, the synthesis of the photochromic compound of the formula (1) will be described. A method similar to that described in International Publication No. WO2019 / 013249 can be suitably used, in which a block polymer having a reactive substituent such as an OH group at the terminal is synthesized in advance.

[0087] In addition to the block polymer having a reactive substituent, a compound having a photochromic moiety and having at least a group capable of reacting with the reactive substituent introduced into the photochromic moiety is synthesized. Preferably, this group is the group that forms L1.

[0088] The reactive substituent of the block polymer is then reacted with the group capable of forming L1 to produce a photochromic compound. The photochromic moiety and the reactive substituent may be reacted directly (in this case, L1 is a direct bond).

[0089] The reactive substituent of the block polymer compound and the group capable of forming L1 are not particularly limited. Alternatively, the OH group of the block polymer compound can be converted to another reactive group by a known method, and then the block polymer compound can be reacted with a compound having a photochromic moiety to which a group capable of reacting with the reactive group has been introduced. For example, L1 can be formed by esterification with a photochromic compound (moiety) having a carboxylic acid terminal. Specifically, the esterification reaction can be carried out in the presence of a mineral acid such as sulfuric acid or hydrochloric acid, an organic acid such as aromatic sulfonic acid, or a Lewis acid such as boron fluoride ether, by stirring in a solvent such as toluene, with heating as necessary, and removing the resulting water by azeotropy. Methods for removing water in the esterification reaction include removing water using a drying agent such as anhydrous magnesium sulfate or molecular sieves, or removing water in the presence of a dehydrating agent such as dicyclohexylcarbodiimide.

[0090] Alternatively, L1 can be formed by esterification with a compound having a terminal carboxylic acid halide. Specifically, a method can be employed in which the compound is stirred in an ether solvent such as tetrahydrofuran in the presence of a base such as pyridine or dimethylaniline, while heating as necessary, and the resulting hydrogen halide is removed.

[0091] Furthermore, L1 can also be formed by esterification with a compound having an acid anhydride terminal, for example, by stirring in a solvent such as toluene in the presence of a catalyst such as sodium acetate or pyridine, while heating as necessary.

[0092] Alternatively, L1 can be formed by a urethanization reaction with a compound having an NCO group at the end. Specifically, this can be achieved by stirring the resulting mixture in the presence of an amine catalyst such as triethylenediamine or a tin catalyst such as dibutyltin dilaurate, either without a solvent or in a solvent such as toluene, while heating as necessary.

[0093] Alternatively, L1 can be formed by Michael addition reaction with a compound having a terminal SH group or a primary or secondary amino group. Specifically, this can be achieved by stirring in the presence of a catalytic amount of a tertiary amine such as triethylamine, a base such as a metal alkoxide, or a solid catalyst such as alumina, without solvent or in a solvent such as toluene, with heating as necessary.

[0094] Another method for synthesizing a photochromic compound involves synthesizing a polymer that has a photochromic moiety and a terminal reactive substituent such as an OH group. Alternatively, a polymer having a group capable of reacting with the reactive substituent is synthesized separately from the polymer having a photochromic moiety and a reactive substituent. This group is preferably a group that forms L2. The reactive substituent of the polymer having a photochromic moiety and a reactive substituent is then reacted with the group capable of forming L2 to form a block polymer, thereby producing the photochromic compound. The reactive substituent and the group capable of forming L2 are not particularly limited. Naturally, as described above, the OH group can also be converted to another reactive group by a known method, and then reacted with a polymer having a group capable of reacting with the reactive group to form a block polymer. The photochromic compound represented by the formula (2) can also be produced by the above-mentioned method.

[0095] <Identification of photochromic compounds> Photochromic compounds generally exist as solids or viscous liquids at room temperature and pressure, and can be confirmed by the following means: Specifically, by a separation procedure such as thin layer chromatography, silica gel column chromatography, high performance liquid chromatography, or gas chromatography, it is confirmed that there are no by-products such as raw material compounds and coloring matters other than the photochromic compound.

[0096] The obtained photochromic compound was analyzed by proton nuclear magnetic resonance spectroscopy ( 1 When measured by H-NMR, peaks due to aromatic protons and alkene protons appear around δ: 5.0 to 9.0 ppm, and peaks due to alkyl and alkylene protons appear around δ: 1.0 to 4.0 ppm. Furthermore, by comparing the relative intensities of each spectrum, the number of protons in each bond group can be determined.

[0097] Photochromic compounds are highly soluble in common organic solvents such as toluene, chloroform, tetrahydrofuran, etc. When the photochromic compound represented by formula (1) or (2) is dissolved in such a solvent, the solution is generally nearly colorless and transparent, and exhibits good photochromic properties, quickly developing color when irradiated with sunlight or ultraviolet light and quickly returning to its original colorless state when the light is blocked.

[0098] <How to use photochromic compounds> Photochromic compounds can be widely used as photochromic materials (photochromic optical articles), and can be used, for example, as various memory materials such as various memory materials replacing silver halide photosensitive materials, copying materials, printing photoreceptors, memory materials for cathode ray tubes, photosensitive materials for lasers, and photosensitive materials for holography. Additionally, photochromic materials using photochromic compounds can also be used as photochromic optical articles such as photochromic lens materials, optical filter materials, display materials, actinometers, and decorations. The photochromic optical articles can be produced, for example, by curing a photochromic curable composition containing a photochromic compound and a polymerizable compound, as described below. Alternatively, optical articles can be produced by laminating a cured layer containing a dispersed photochromic compound on the surface of a substrate such as a plastic lens.

[0099] Because photochromic compounds exhibit excellent photochromic properties even in solid matrices, they can be dispersed in a polymer solid matrix for use, or they can be used to form polymer molded articles with the photochromic compound dispersed therein. Dispersion methods that are well known in the art can be used. For example, a method in which a photochromic compound and a solid matrix such as a thermoplastic resin are kneaded in a molten state to disperse the photochromic compound in the solid matrix, a method in which a polymeric photochromic compound is dissolved in a polymerizable compound, a polymerization catalyst is added, and the mixture is cured by heat or light to disperse the photochromic compound in the cured product, or a method in which a polymeric photochromic compound is dyed on the surface of the solid matrix to disperse the photochromic compound in the solid matrix, etc.

[0100] Examples of the solid matrix include optically preferable polyacrylates, polymethacrylates, poly(C l -C l2 ) alkyl methacrylates, polyoxy(alkylene methacrylate), poly(alkoxylated phenol methacrylate), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(vinylpyrrolidone), poly((meth)acrylamide), poly(dimethylacrylamide), poly(hydroxyethyl methacrylate), poly((meth)acrylic acid), thermoplastic polycarbonates, polyesters, polyurethanes, polythiourethanes, poly(ethylene terephthalate), polystyrene, and poly(α-methylstyrene).

[0101] For example, when a photochromic compound is used in a photochromic lens, any method that can achieve uniform photochromic performance is acceptable. Examples include sandwiching a polymer film containing a uniformly dispersed photochromic compound within the lens; dispersing the photochromic compound in a polymerizable compound and polymerizing it using a predetermined method; or dissolving the photochromic compound in, for example, silicone oil and impregnating the lens surface at 150 to 200°C for 10 to 60 minutes, followed by coating the surface with a curable substance to produce a photochromic lens. Another method that can be used is to apply the above-mentioned polymer film to the lens surface and then coat the surface with a curable substance to produce a photochromic lens. Furthermore, a coating agent composed of a photochromic compound-curable composition containing the photochromic compound described below can be applied to the surface of the lens substrate, and the coating film can be cured. In this case, the lens substrate may be previously subjected to a surface treatment such as an alkaline solution or plasma treatment. Furthermore, a primer can be applied to improve adhesion between the substrate and the coating film, either in conjunction with or without these surface treatments.

[0102] <Photochromic curable composition> By blending a photochromic compound with a polymerizable compound, the composition can be used as a photochromic curable composition. The photochromic compound may be used alone, or may be combined with other photochromic compounds depending on the purpose, for example, to obtain various color tones required for a photochromic lens. The photochromic compound to be combined can be any known photochromic compound without any limitations. Examples include naphthopyran, spirooxazine, spiropyran, fulgide, fulgimide, etc. Among these, naphthopyran is preferred, and indenonaphthopyran is particularly preferred, from the viewpoints of maintaining a uniform color tone during color development and fading, suppressing color shift during color development due to deterioration of the photochromic compound, and further suppressing initial coloring. Furthermore, from the viewpoint of suppressing color shift during color development and fading due to differences in matrix dependency, it is preferable that the other photochromic compound also be a photochromic compound having an oligomer chain group. Furthermore, when using a photochromic compound having an oligomer chain group, it is most preferable to use multiple photochromic compounds to adjust the color tone, from the viewpoint of suppressing cloudiness of the cured product.

[0103] In the photochromic curable composition, the amount of the photochromic compound is not particularly limited and may be appropriately selected taking into consideration the color development intensity of the photochromic compound and the thickness of the resulting photochromic cured product. Specifically, the amount of the photochromic compound containing the photochromic compound is preferably 0.0001 to 30 parts by mass, more preferably 0.0003 to 20 parts by mass, and most preferably 0.0005 to 10 parts by mass, per 100 parts by mass of the polymerizable compound.

[0104] Since the color intensity of a photochromic cured body depends on the thickness of the cured body, it is particularly important to take the thickness into consideration. For example, when a thin film of 100 μm or less is formed using a photochromic curable composition, it is preferable to adjust the color tone by using 0.001 to 10 parts by mass of a photochromic compound containing a polymeric photochromic compound per 100 parts by mass of the polymerizable compound. Furthermore, when a photochromic cured body having a thickness of 1 mm or more is produced, it is preferable to adjust the color tone by using 0.0005 to 5 parts by mass of a photochromic compound containing a polymeric photochromic compound per 100 parts by mass of the polymerizable compound.

[0105] <Polymerizable compound> As described above, a photochromic compound can be combined with a polymerizable compound to form a photochromic curable composition. Examples of the polymerizable compound include urethane or urea-based polymerizable compounds capable of forming urethane bonds, urea bonds, and the like, radically polymerizable compounds, and epoxy-based polymerizable compounds. These polymerizable compounds are not particularly limited, but for example, the polymerizable compounds described in International Publication WO 2018-235771 are preferably used. Among these, the following urethane-based polymerizable compounds or radically polymerizable compounds are particularly preferably used.

[0106] (urethane-based polymerizable compound) As the urethane-based polymerizable compound, a composition containing an isocyanate compound and a compound having active hydrogen can be suitably used. Note that the isocyanate compound refers to a compound having an isocyanate group or an isothiocyanate group, and may be a compound having both an isocyanate group and an isothiocyanate group.

[0107] Any known iso(thio)cyanate compound can be used without any particular limitation, but it is preferable that the compound contains a polyiso(thio)cyanate group having at least two iso(thio)cyanate groups in one molecule, and it is particularly preferable that the compound contains a polyiso(thio)cyanate compound having an aromatic ring, such as m-xylene diisocyanate or 4,4'-diphenylmethane diisocyanate, or an aliphatic polyiso(thio)cyanate compound, such as norbornane diisocyanate or dicyclohexylmethane-4,4'-diisocyanate.

[0108] The compound having active hydrogen can be used without any particular limitation, but is preferably a compound having an amino group and / or a hydroxyl group and / or a thiol group. It is particularly preferable to include a polyfunctional compound having two or more active hydrogen atoms per molecule. Specific examples of the compound having active hydrogen include bifunctional amine compounds such as isophorone diamine, bis-(4-aminocyclohexyl)methane, and norbornane diamine; polyfunctional thiol compounds such as dipentaerythritol hexakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and 4-mercaptomethyl-3,6-dithia-octanedithiol; and polyfunctional alcohols such as trimethylolpropane and pentaerythritol. Compositions containing these compounds are preferred.

[0109] Furthermore, in consideration of the durability of the resulting photochromic cured product, it is preferable to use an active hydride having at least one piperidine structure, hindered phenol structure, triazine structure, or benzotriazole structure in the molecule.

[0110] (Radical polymerizable compound) The radical polymerizable compound can be classified into a polyfunctional radical polymerizable compound and a monofunctional radical polymerizable compound, and each can be used alone or in combination. The radical polymerizable substituent includes a group having an unsaturated double bond, that is, a vinyl group (including a styryl group, a (meth)acrylic group, an allyl group, etc.).

[0111] A polyfunctional radical polymerizable compound refers to a compound having two or more radical polymerizable substituents in the molecule. This polyfunctional radical polymerizable compound can be divided into a first polyfunctional radical polymerizable compound having 2 to 10 radical polymerizable substituents and a second polyfunctional radical polymerizable compound having more than 10 radical polymerizable substituents.

[0112] The first polyfunctional radical polymerizable compound is not particularly limited, but more preferably has 2 to 6 radical polymerizable substituents. Specifically, examples of the first polyfunctional radical polymerizable compound include polyfunctional (meth)acrylic acid ester compounds such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol bisglycidyl (meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, and 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane; Examples of suitable allyl compounds include polyfunctional allyl compounds such as allyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, and trimethylolpropane triallyl carbonate; polyfunctional thio(meth)acrylic acid ester compounds such as 1,2-bis(methacryloylthio)ethane, bis(2-acryloylthioethyl)ether, and 1,4-bis(methacryloylthiomethyl)benzene; and vinyl compounds such as divinylbenzene.

[0113] Examples of the second polyfunctional radically polymerizable compound include compounds with a relatively large molecular weight, such as silsesquioxane compounds having a radically polymerizable substituent and polyrotaxane compounds having a radically polymerizable substituent.

[0114] The monofunctional radical polymerizable compound refers to a compound having one or more radical polymerizable substituents in the molecule. Examples of the monofunctional radical polymerizable compound include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride; methyl (meth)acrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxy methacrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate, 3-(glycidyloxy-1-isopropyl (meth)acrylic acid ester compounds such as 3-glycidyloxy-2-hydroxypropyl acrylate and 3-glycidyloxy-2-hydroxypropyl acrylate; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid ester compounds such as methyl thioacrylate, benzyl thioacrylate and benzyl thiomethacrylate; and vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer and bromostyrene.

[0115] The radical polymerizable compounds can be used alone or in combination. In this case, the amount of the polyfunctional radical polymerizable compound is preferably 80 to 100 parts by mass and the amount of the monofunctional radical polymerizable compound is preferably 0 to 20 parts by mass per 100 parts by mass of the total radical polymerizable compounds. More preferably, the amount of the polyfunctional radical polymerizable compound is 90 to 100 parts by mass and the amount of the monofunctional radical polymerizable compound is 0 to 10 parts by mass. Furthermore, the amount of the first polyfunctional radical polymerizable compound is preferably 80 to 100 parts by mass, the amount of the second radical polymerizable compound is 0 to 20 parts by mass, and the amount of the monofunctional radical polymerizable compound is 0 to 20 parts by mass per 100 parts by mass of the total radical polymerizable compounds. More preferably, the amount of the first polyfunctional radical polymerizable compound is 85 to 100 parts by mass, the amount of the second polyfunctional radical polymerizable compound is 0 to 10 parts by mass, and the amount of the monofunctional radical polymerizable compound is 0 to 10 parts by mass.

[0116] <Other additives> The photochromic curable composition may contain various known additives, such as various stabilizers, additives, solvents, and leveling agents, including release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances, as well as thiols such as t-dodecyl mercaptan as polymerization regulators, as needed, within the range that does not impair the effects of the composition.

[0117] Among these, the use of an ultraviolet stabilizer is preferred because it can improve the durability of the photochromic moiety. Known examples of such ultraviolet stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants. Particularly preferred ultraviolet stabilizers are as follows: Examples of suitable terpolymers include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, and LA-87 manufactured by Asahi Denka Kogyo Co., Ltd., 2,6-di-tert-butyl-4-methylphenol, and ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], and IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, and 565 manufactured by Ciba Specialty Chemicals.

[0118] The amount of such ultraviolet stabilizer used is not particularly limited as long as it does not impair the effect, but is usually 0.001 to 10 parts by mass, and preferably 0.01 to 5 parts by mass, per 100 parts by mass of the photochromic curable composition.

[0119] In addition to the UV stabilizer, a UV absorber can also be used. Examples of UV absorbers that can be used include known UV absorbers such as benzotriazole-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, cyanoacrylate-based UV absorbers, diphenylacrylate-based UV absorbers, phenol-based UV absorbers, oxanilide-based UV absorbers, malonic acid ester-based UV absorbers, and cinnamic acid ester-based UV absorbers. Cyanoacrylate-based UV absorbers, benzophenone-based UV absorbers, oxanilide-based UV absorbers, malonic acid ester-based UV absorbers, and cinnamic acid ester-based UV absorbers are particularly preferred, with oxanilide-based UV absorbers, malonic acid ester-based UV absorbers, and cinnamic acid ester-based UV absorbers being particularly preferred. The UV stabilizer is preferably used in an amount of 0.001 to 5 parts by mass per 100 parts by mass of the photochromic curable composition.

[0120] The photochromic curable composition may contain polymerizable compounds other than those mentioned above within the range that does not impair the effects, and the blending ratio may be determined appropriately depending on the application.

[0121] <Method of using photochromic curable composition; photochromic optical article> The photochromic curable composition can be polymerized to obtain a cured product, which can be used as a photochromic optical article. The photochromic curable composition can be prepared by mixing the photochromic compound, polymerizable compound, and additives to be used as needed using a known method. Polymerization to produce the cured product is carried out by radical polymerization, ring-opening polymerization, anionic polymerization, or condensation polymerization using irradiation with active energy rays such as ultraviolet rays, α-rays, β-rays, or γ-rays, heat, or a combination of both. That is, an appropriate polymerization method can be adopted depending on the type of polymerizable compound and polymerization curing accelerator and the form of the cured product to be formed.

[0122] When thermally polymerizing a photochromic curable composition, the temperature in particular affects the properties of the resulting cured product. The temperature conditions cannot be generally limited because they are affected by the type and amount of the thermal polymerization initiator and the type of polymerizable compound. However, a method in which polymerization is initiated at a relatively low temperature and the temperature is slowly increased is generally preferred. Like the temperature, the polymerization time also varies depending on various factors. Therefore, it is preferable to determine the optimal time in advance based on these conditions. Generally, it is preferable to select conditions so that polymerization is completed within 2 to 48 hours.

[0123] Furthermore, when photopolymerizing a photochromic curable composition, among the polymerization conditions, UV intensity in particular affects the properties of the resulting cured product. The illuminance conditions cannot be generally limited because they are affected by the type and amount of the photopolymerization initiator and the type of polymerizable monomer, but generally, they are 50 to 500 mW / cm at a wavelength of 365 nm. 2 It is preferable to select the conditions so that the UV light is irradiated for 0.5 to 5 minutes.

[0124] For example, when the cured product is to be used as a photochromic lens, any of the known methods described below can be used as long as it can provide uniform photochromic performance.

[0125] When the photochromic lens is produced by the kneading method, the photochromic curable composition is injected between glass molds held by elastomer gaskets or spacers, and depending on the types of polymerizable compound and polymerization curing accelerator, cast polymerization is carried out by heating in an air oven or irradiating with active energy rays such as ultraviolet rays, to obtain a photochromic optical article molded into the shape of a lens or the like.

[0126] When manufacturing a photochromic lens by the lamination method, a coating liquid is prepared by dissolving a photochromic curable composition in an appropriate organic solvent, and the coating liquid is applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping, or the like, and then dried to remove the organic solvent. Subsequently, polymerization is carried out by UV irradiation or heating in an inert gas such as nitrogen, thereby obtaining a photochromic lens having a photochromic layer formed on the surface of the optical substrate (coating method).

[0127] Alternatively, an optical substrate such as a lens substrate is arranged so that a predetermined gap is formed, a photochromic curable composition is injected into this gap, and then, in this state, polymerization is carried out by UV irradiation, heating, or the like using an inner mold, thereby obtaining a photochromic lens having a photochromic layer formed on the surface of the optical substrate (cast polymerization method).

[0128] When forming a photochromic layer on the surface of an optical substrate by the above-mentioned lamination methods (coating method and cast polymerization method), the adhesion between the photochromic layer and the optical substrate can be improved by previously subjecting the surface of the optical substrate to a chemical treatment using an alkaline solution, an acid solution, etc., or a physical treatment using corona discharge, plasma discharge, polishing, etc. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

[0129] Furthermore, when producing a photochromic lens by the binder method, first, a photochromic sheet is produced by sheet molding using a photochromic curable composition, and this is sandwiched between two transparent sheets (optical sheets), and the polymerization described above is carried out to obtain a photochromic laminate in which the photochromic layer serves as an adhesive layer.

[0130] In this case, the photochromic sheet can also be produced by coating with a coating liquid prepared by dissolving the photochromic curable composition in an organic solvent.

[0131] The photochromic laminate thus produced is placed in a mold, and then a thermoplastic resin (e.g., polycarbonate) for optical substrates such as lenses is injection molded to obtain a photochromic lens of a predetermined shape on which the photochromic laminate is laminated. The photochromic laminate can also be adhered to the surface of an optical substrate with an adhesive or the like, thereby obtaining a photochromic lens.

[0132] When preparing a photochromic laminate as described above, it is preferable to use a urethane or urea-based polymerizable compound, particularly a urethane-based polymerizable compound, as the polymerizable compound, and adjust it so that polyurethane is formed, in view of particularly high adhesion to the optical substrate.

[0133] The cured product obtained by polymerizing the above-described photochromic curable composition can exhibit excellent photochromic properties, with high color density even at high temperatures.

[0134] Furthermore, the cured product obtained by polymerizing the photochromic curable composition can be subjected to post-processing depending on its application, such as dyeing with a dye such as a disperse dye, forming a hard coating film using a hard coating agent whose main component is a silane coupling agent or a sol of silicon, zirconium, antimony, aluminum, tin, tungsten, or the like, forming a thin film by vapor deposition of a metal oxide such as SiO2, TiO2, or ZrO2, or applying an organic polymer to form a thin film to provide anti-reflection treatment, anti-static treatment, or the like. [Example]

[0135] Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples.

[0136] The number of repeating units of the polymers specified in the examples is an average value determined using proton nuclear magnetic resonance spectroscopy.

[0137] Example 1 1st step 75 g (10 mmol) of polyethylene glycol monomethyl ether with a number average molecular weight of 750, 100 mL of dichloromethane, and succinic anhydride (1.5 g, 15 mmol) were added and stirred. Triethylamine (2.0 g, 20 mmol) was added thereto, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, 10% hydrochloric acid was added to the reaction solution after ice-water bathing, and the layers were separated. The solvent was distilled off from the organic layer to obtain the compound represented by the following formula (7):

[0138] [ka] The number of repeating units such as polyoxyethylene groups and polyoxypropylene groups varies during the reaction or purification process, and in this example, the number of repeating units after the reaction or purification in each step is shown.

[0139] 2nd process 4.3 g (5.0 mmol) of the compound of the formula (7), [ka] 5.5 g (4.9 mmol) of the compound represented by the formula (I) and 20 mL of dichloromethane were added and stirred, and then 192 mg of WSC (water-soluble carbodiimide) and 63 mg of DMAP (dimethylaminopyridine) were added and stirred for 12 hours.

[0140] After the reaction was completed, 10 mL of water was added and the layers were separated. Anhydrous magnesium sulfate was added to the organic layer and dried, after which the magnesium sulfate was filtered off and the solvent of the obtained filtrate was concentrated. After concentration, 15 mL of tetrahydrofuran was added and stirred, and while cooling with ice water, 7.5 mL of tetrabutylammonium fluoride (1 mM tetrahydrofuran solution) was added and stirred for 12 hours. After the reaction was completed, water was added and the layers were separated. The solvent of the obtained organic layer was concentrated and purified by silica gel column chromatography to obtain a compound represented by the following formula (9):

[0141] [ka] The compound represented by the formula:

[0142] 3rd process The same operation as in the first step is carried out to add succinic anhydride to the compound of formula (9) to obtain the compound of formula (10) [ka] The compound represented by the formula:

[0143] 4th step The following formula (11) [ka] 4.62 g (10 mmol) of a compound represented by the following formula (12): [ka] 100 mL of toluene was added to 4.48 g (15 mmol) of a compound represented by the formula: and 0.25 g (1.0 mmol) of pyridinium p-toluenesulfonate, and the mixture was heated and stirred at 75° C. for 2 hours. After cooling to room temperature, 100 mL of water was added and the mixture was separated. The solvent in the resulting organic layer was concentrated and purified by silica gel column chromatography to obtain a compound represented by the formula (13): [ka] A chromene compound represented by the following formula was obtained.

[0144] 5th step 1.56 g (2.1 mmol) of the chromene compound represented by the formula (13) and 4.24 g (2.0 mmol) of the compound represented by the formula (10) were added to 20 mL of dichloromethane and stirred, and then 380 mg of WSC and 120 mg of DMAP were added and stirred while shielded from light. After the reaction was completed, 10 mL of water was added, and the mixture was separated. The solvent in the resulting organic layer was concentrated and purified by silica gel column chromatography to give the compound represented by the following formula (14): [ka] The compound represented by the formula was obtained in a yield of 60%.

[0145] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 21H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, which are derived from the photochromic compound, a peak of approximately 40.5H due to the cyclohexane ring, methyl group, succinic acid moiety, and propyleneoxy protons at around 1.0 to 3.0 ppm, and a 143.7H peak due to the methoxy group, propyleneoxy group, and ethyleneoxy at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (14).

[0146] <Example 2> 1st step 35.0 g (50.0 mmol) of polypropylene glycol having a number average molecular weight of 700, 6.31 g (62.5 mmol) of triethylamine, and 1 L of dichloromethane were added and cooled on ice. 5.43 g (60.0 mmol) of acryloyl chloride was slowly added dropwise over 1 hour. After the reaction was completed, 1 L of water was added and the mixture was separated. The resulting organic layer was concentrated and purified by silica gel column chromatography to obtain polypropylene glycol monoacrylate having a number average molecular weight of 700.

[0147] 2nd process 14.1 g (18.7 mmol) of polypropylene glycol monoacrylate having a number average molecular weight of 700, 7.0 mg of dibutylhydroxytoluene (BHT), 2.0 g (20.0 mmol) of succinic anhydride, and 500 mL of dichloromethane were added, and 2.52 g (25 mmol) of triethylamine was slowly added while stirring under ice cooling. After stirring for 12 hours, 200 mL of water was added, and the mixture was separated. The solvent in the obtained organic layer was concentrated, and the product was obtained by the following formula (15) [ka] The compound represented by the formula:

[0148] 3rd process The following formula (16) [ka] 3.61 g (5.0 mmol) of a chromene compound represented by the formula (15) and 4.19 g (4.9 mol) of the compound represented by the formula (15) were added to 50 mL of dichloromethane and stirred, and then 950 mg of WSC and 300 mg of DMAP were added and stirred while shielded from light. After the reaction was completed, 30 mL of water was added, and the mixture was separated. The solvent in the resulting organic layer was concentrated and purified by silica gel column chromatography to give the compound represented by the formula (17) [ka] The compound represented by the formula was obtained in a yield of 85%.

[0149] 4th step 6.76 g (4.2 mmol) of the compound represented by the formula (17) was dissolved in 30 mL of toluene, and 1.29 g (4.5 mmol) of 1-octadecanethiol and 5 g of neutral alumina were added thereto, followed by stirring at room temperature. After the reaction was completed, the neutral alumina was filtered off, and the solvent in the resulting organic layer was concentrated and purified by silica gel column chromatography to obtain a compound represented by the following formula (18): [ka] The compound represented by the formula was obtained in a yield of 90%.

[0150] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 17H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, which are derived from the photochromic compound, a peak of approximately 96.5H due to the cyclohexane ring, octadecyl group, succinic acid moiety, and propyleneoxy protons at around 1.0 to 3.0 ppm, and a 56.5H peak due to the methoxy group, propyleneoxy group, ethyleneoxy group, and morpholino group at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (18).

[0151] Example 3 1st step 40.0 g (100.0 mmol) of polyethylene glycol monoethyl ether having a number average molecular weight of 400 and 21.0 g (110.0 mmol) of toluenesulfonyl chloride were dissolved in 500 ml of pyridine. Under ice cooling and stirring, 2.2 g (20.0 mmol) of 1,4-diazabicyclo[2.2.2]octane was added with 2.2 g (20.0 mmol), and the mixture was stirred for 12 hours while the temperature was raised to room temperature. After the reaction was completed, the reaction solution was added to ice water and extracted with dichloromethane. The resulting organic layer was dried over anhydrous magnesium sulfate and filtered. The solvent in the resulting organic layer was concentrated and purified by silica gel column chromatography to give the compound represented by the following formula (19): [ka] The compound represented by the formula:

[0152] 2nd process To a mixture of 5.44 g (40.0 mmol) of 2-(methoxymethoxy)-1,3-propanediol, 100 mL of diethylformamide (DMF), and 4.0 g (100.0 mmol) of sodium hydride (containing 40% mineral oil) was added 49.87 g (90.0 mol) of the compound of formula (19) while stirring under ice cooling, and the mixture was allowed to react for 24 hours. After the reaction, 300 mL of water, 500 mL of THF, and 500 mL of toluene were added, and the mixture was separated. The resulting organic layer was dried over anhydrous magnesium sulfate and filtered. The solvent in the resulting organic layer was concentrated and purified by silica gel column chromatography.

[0153] 200 mL of methanol and 50 mL of hydrochloric acid were added thereto, and the mixture was stirred at room temperature for 24 hours. After the reaction, the mixture was neutralized with sodium bicarbonate, and then the methanol was concentrated. 500 mL of ethyl acetate and 200 mL of water were added, and the mixture was separated. The obtained organic layer was dried over anhydrous magnesium sulfate and filtered. The solvent in the obtained organic layer was concentrated and purified by silica gel column chromatography to obtain a compound represented by the following formula (20): [ka] The compound represented by the formula:

[0154] 3rd process The same reaction as in the first step of Example 1 was carried out using the compound of formula (20) to obtain a compound of formula (21) [ka] The compound represented by the formula:

[0155] 4th step In the second step of Example 1, the compound of the formula (7) was replaced with the compound of the formula (21), and the compound of the formula (8) was replaced with the compound of the following formula (22): [ka] The reaction was carried out in the same manner except that the following formula (23) was used: [ka] The compound represented by the formula:

[0156] 5th step The same reaction as in the first step of Example 1 was carried out using the compound of formula (23) to give the compound of formula (24) [ka] The compound represented by the formula:

[0157] 6th step Instead of the above formula (13), the following formula (25) [ka] The same procedure as in the fifth step of Example 1 was carried out except that a compound represented by the formula (24) was used instead of the compound represented by the formula (10), to obtain a compound represented by the following formula (26): [ka] The compound represented by the formula was obtained in a yield of 65%.

[0158] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 16H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, which are derived from the photochromic compound, a peak of approximately 136.2H due to cyclooctane ring, succinic acid moiety, and propyleneoxy protons at around 1.0 to 3.0 ppm, and a 207.2H peak due to methoxy group, propyleneoxy group, ethyleneoxy group, morpholino group, and glycerol group at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (26).

[0159] Example 4 The same procedure as in the second step of Example 1 was carried out, except that 17.1 g (50.0 mmol) of eicosanedioic acid and 37.5 g (50.0 mmol) of polyethylene glycol monomethyl ether having a number average molecular weight of 750 were used, to obtain a compound represented by the following formula (27): [ka] The compound represented by the formula:

[0160] 2nd process The reaction was carried out in the same manner as in Example 3, except that the compound of formula (27) was used instead of the compound of formula (21) in the fourth step, to obtain the compound of formula (28) below.

[0161] [ka] The compound represented by the formula:

[0162] 3rd process The product of the second step was used to carry out the same reaction as in the first step of Example 1 to obtain the compound represented by the following formula (29): [ka] The compound represented by the formula:

[0163] 4th step In the fourth step of Example 1, instead of the compound of formula (11), a compound of the following formula (30) [ka] The same procedure was carried out except that a compound represented by the following formula (31) was used. [ka] A chromene compound represented by the following formula was obtained.

[0164] 5th step The compound of formula (29) obtained in the third step and the compound of formula (31) obtained in the fourth step are reacted in the same manner as in the fifth step of Example 1 to give the compound of formula (32):

[0165] [ka] The compound represented by the formula was obtained in a yield of 69%.

[0166] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, the photochromic compound exhibited a 16H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, while the cyclooctane ring, succinic acid moiety, and propyleneoxy proton-derived peaks at around 1.0 to 3.0 ppm exhibited a 148.9H peak due to methoxy groups, propyleneoxy groups, and ethyleneoxy groups at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (32).

[0167] <Example 5> 1st step The same procedure as in Example 1 was carried out, except that lignoceric acid was used instead of the compound of formula (7), to obtain a compound of formula (33) [ka] The compound represented by the formula:

[0168] 2nd process In the fifth step of Example 1, the compound of the formula (33) was used instead of the compound of the formula (10), and the compound of the formula (34) was used instead of the compound of the formula (13). [ka] The reaction was carried out in the same manner except that the compound of formula (35) was used. [ka] The compound shown was obtained in 72% yield.

[0169] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, the photochromic compound exhibited a 19H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, while the photochromic compound exhibited a peak of approximately 130.5H due to cyclohexane ring, succinic acid moiety, and propyleneoxy protons at around 1.0 to 3.0 ppm, and a 76.5H peak due to morpholino group, methoxy group, propyleneoxy group, and ethyleneoxy group at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (35).

[0170] (Production and evaluation of cured products (thiourethane-based molded products)) A photochromic curable composition was prepared by mixing the components according to the following formulation. The amounts of each component are shown below. Table 1 shows the photochromic properties of the cured products obtained using the photochromic compounds of Examples 1 to 5.

[0171] (Composition of polymerizable compounds) m-Xylene diisocyanate: 43.1 parts by mass Pentaerythritol tetrakis(3-mercaptopropionate): 49.7 parts by mass 1-decanethiol: 2.7 parts by mass RX-1 prepared by the method described in International Publication WO2016 / 143910: 4.5 parts by mass Dimethyldichlorotin: 0.05 parts by mass JP-506H (manufactured by Johoku Chemical Industry Co., Ltd.): 0.1 parts by mass 0.1 parts by mass of ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]

[0172] <Examples 6 to 10 and Comparative Examples 1 to 3> The photochromic curable composition was prepared by adding a photochromic compound to the above-mentioned polymerizable compound formulation so that the photochromic moiety was 0.53 μmol per 100 g of polymerizable compound. The photochromic curable composition thus obtained was polymerized by a kneading method to obtain a photochromic cured product. The polymerization method is as follows. (Polymerization method) After thoroughly degassing the photochromic curable composition, it was poured into a 2 mm thick mold consisting of a glass mold and a gasket made of ethylene-vinyl acetate copolymer. The temperature was gradually increased from 25°C to 70°C, allowing it to cure for 24 hours. After polymerization was complete, the photochromic cured product was removed from the glass mold and annealed at 100°C for 1 hour.

[0173] (Hardened body; Evaluation method) The obtained cured body was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Inc. was irradiated through an Aeromass filter (manufactured by Corning) at 20±1°C, with a beam intensity of 365 nm = 2.4 mW / cm on the surface of the cured body. 2 , 245nm=24μW / cm 2 The photochromic properties of the cured product were measured.

[0174] The photochromic properties and the cloudiness of the cured product were evaluated by the following methods. (1) Photochromic properties Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development, determined using a spectrophotometer (instant multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone during color development. Color density {ε(300)-ε(0)}: The difference between the absorbance {ε(300)} after 300 seconds of light irradiation and the absorbance ε(0) before light irradiation at the maximum absorption wavelength. The higher this value, the better the photochromic properties. ·Fading speed〔t1 / 2(sec.)〕: The time required for the absorbance of a sample at the maximum absorption wavelength to decrease to half of {ε(300) - ε(0)} after 300 seconds of light irradiation and then the light irradiation is stopped. The shorter this time, the better the photochromic properties.

[0175] (2) Cloudy The molded cured product was visually evaluated for cloudiness. 1: No turbidity can be seen with the naked eye, and no turbidity can be seen even when light is transmitted through it. 2: No turbidity can be seen with the naked eye, but a slight turbidity can be seen when light is passed through it. 3: No visible turbidity, but when light is passed through it, the turbidity is more pronounced than in 2. 4: Slight cloudiness can be seen with the naked eye 5: Cloudiness is clearly visible even to the naked eye.

[0176] (Comparative Example Compound) In Comparative Examples 1 to 4, photochromic compounds having the following structures were used.

[0177] (Comparative Examples 1 and 4) [ka]

[0178] (Comparative Example 2) [ka]

[0179] (Comparative Example 3) [ka]

[0180] [Table 1]

[0181] In Table 1, the column labeled "Maximum Absorption Wavelength" lists the positions (wavelengths) of the two peaks that appeared in the optical spectrum. The peak that appeared at the shorter wavelength of the two peaks is designated the first peak, and its wavelength is listed in the upper row of the cell. The peak that appeared at the longer wavelength of the second peak is designated the second peak, and its wavelength is listed in the lower row of the cell. In the column labeled "23°C Color Density," the 23°C color density of the first peak is listed in the upper row of the cell, and the 23°C color density of the second peak is listed in the lower row. In the column labeled "23°C Fade Rate," the 23°C fading rate of the first peak is listed in the upper row of the cell, and the 23°C fading rate of the second peak is listed in the lower row. The same applies to Tables 2 to 4.

[0182] As is clear from Table 1, the photochromic compound of the present invention exhibits superior photochromic properties compared to the photochromic compound of Comparative Example 1 which does not have an oligomer chain group.

[0183] It is also clear that aggregation of the photochromic compound is suppressed compared to the photochromic compound of Comparative Example 2 which contains only a polyoxypropylene chain group.

[0184] The photochromic compound of Comparative Example 3 having a random polymer type oligomer chain group with polyethylene glycol has improved compatibility (dispersibility in a solid matrix) and suppressed cloudiness compared to the photochromic compound of Comparative Example 2 having only a polypropylene glycol chain. However, in the case of the random type polymer, the formation of a microphase separation structure is insufficient, and therefore the dispersibility is inferior to the photochromic compound of Example 1 having a block oligomer chain group with polyethylene glycol.

[0185] As is clear from these results, the photochromic compound of the present invention has excellent photochromic properties and also excellent dispersibility even in a solid matrix.

[0186] Example 11 The reaction was carried out in the same manner as in Example 1, except that polyethylene glycol monocetyl ether having a number average molecular weight of 770 was used instead of polyethylene glycol monomethyl ether having a number average molecular weight of 750, to obtain a compound represented by the following formula (39): [ka] The compound represented by the formula was obtained in a yield of 65%.

[0187] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 21H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, which are derived from the photochromic compound, a 52H peak due to protons of the cyclohexane ring, methyl group, succinic acid moiety, and hexadecyl group at around 1.0 to 3.0 ppm, and a peak of approximately 58.4H due to methoxy group, propyleneoxy group, and ethyleneoxy at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (39).

[0188] Example 12 1st step The following formula (40) [ka] 115.4 g (100.0 mmol) of a compound represented by the formula: ##STR1## 1000 mL of DMF and 17.0 g (250.0 mmol) of imidazole were added and stirred under ice cooling. 14.9 g (99.0 mmol) of tert-butyldimethylchlorosilane dissolved in 150 mL of DMF was slowly added dropwise thereto. After stirring for 12 hours, 1000 mL of water and 1500 mL of toluene were added and the mixture was separated. The solvent in the resulting organic layer was concentrated and purified by silica gel column chromatography to obtain a compound represented by the formula (41) below. [ka] The compound represented by the formula:

[0189] 2nd process Using the formula (41), the same operation as in Example 1 was carried out, The following formula (42) [ka] The compound represented by the formula:

[0190] 3rd process In the fifth step of Example 1, a compound represented by the formula (42) was used instead of the compound represented by the formula (10), and a compound represented by the following formula (43) was used instead of the compound represented by the formula (13). [ka] The same procedure was carried out except that a compound represented by the following formula (44) was used. [ka] The compound represented by the formula was obtained in a yield of 65%.

[0191] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 17H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, which are derived from the photochromic compound, a peak of approximately 100H due to protons of the dimethylsilyl group, succinic acid moiety, and methyl group at around -1.0 to 3.0 ppm, and a peak of approximately 90H due to the methoxy group and ethyleneoxy at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (44).

[0192] (Production and evaluation of hardened products (acrylic molded products)) A photochromic curable composition was prepared by mixing the components according to the following formulation. The amounts of each component are shown below. Table 2 also shows the photochromic properties of the cured products using the photochromic compounds of the Examples listed in Table 2. (Composition of polymerizable compounds) Propylene glycol diacrylate: 45 parts by mass Trimethylolpropane triacrylate: 11 parts by mass Polyethylene glycol diacrylate: 17 parts by mass Kyoeisha Chemical Co., Ltd. UA-306T: 27 parts by mass 0.1 parts by mass of ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] 0.1 parts by weight of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Di-tertiary butyl peroxide: 1.75 parts by mass

[0193] <Examples 13 to 16, Comparative Example 4> The photochromic curable composition was prepared by adding a photochromic compound to the above-mentioned polymerizable compound formulation so that the photochromic moiety was 0.53 μmol per 100 g of polymerizable compound. The photochromic curable composition thus obtained was polymerized by a kneading method to obtain a photochromic cured product. The polymerization method is as follows. (Polymerization method) After thoroughly degassing the photochromic curable composition, it was poured into a 2 mm thick mold consisting of a glass mold and a gasket made of ethylene-vinyl acetate copolymer. The composition was then cured over 24 hours while gradually increasing the temperature from 25°C to 90°C. After polymerization was complete, the cured product was removed from the glass mold and annealed at 100°C for 2 hours. The results are shown in Table 2.

[0194] [Table 2]

[0195] It is clear that the photochromic compound of the present invention exhibits excellent effects even in an acrylic substrate.

[0196] Example 17 1st step The same procedure was carried out as in Example 1, except that polypropylene glycol monobutyl ether having a number average molecular weight of 1,500 was used instead of polyethylene glycol monomethyl ether having a number average molecular weight of 750 in the first step, to obtain a compound represented by the following formula (45): [ka] The compound represented by the formula:

[0197] 2nd process The same procedure was carried out as in Example 12, except that polytetramethylene glycol having a number average molecular weight of 2000 was used instead of the compound of formula (40) in the first step, to obtain a compound represented by the following formula (46): [ka] The compound represented by the formula:

[0198] 3rd process The reaction was carried out in the same manner as in the second step of Example 1, except that the compound of formula (45) was used instead of the compound of formula (7) and the compound of formula (46) was used instead of the compound of formula (8), to obtain a compound represented by the following formula (47): [ka] The compound represented by the formula:

[0199] 4th step The same operation as in the third step of Example 1 was carried out to add succinic anhydride to the formula (47) to obtain the following formula (48): [ka] The compound represented by the formula:

[0200] 5th step The same procedure was carried out as in the third step of Example 2, except that the compound of formula (48) was used instead of the compound of formula (15), to obtain a compound of formula (49) [ka] The compound represented by the following formula was obtained in a yield of 67%.

[0201] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, the photochromic compound exhibited a 17H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, while the photochromic compound exhibited a peak of approximately 149.5H due to protons of the cyclohexane ring, butyl group, succinic acid moiety, propyleneoxy group, and tetramethylene glycol group at around 1.0 to 3.0 ppm, and a peak of 133.5H due to methoxy group, propyleneoxy group, ethyleneoxy group, morpholino group, and tetramethylene glycol group at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (49).

[0202] Example 18 1st step In the third step of Example 17, the compound of the following formula (50) was used instead of the compound of the formula (45). [ka] The reaction was carried out in the same manner except that the compound of formula (51) was used. [ka] The compound represented by the formula:

[0203] 2nd process The same operation as in the fourth step of Example 17 was carried out to add succinic anhydride to the formula (51) to obtain the compound represented by the following formula (52): [ka] The compound represented by the formula:

[0204] 3rd process In the fifth step of Example 1, instead of the chromene compound represented by the formula (13), a compound represented by the following formula (53) [ka] The same procedure was carried out except that a chromene compound represented by the formula (52) was used instead of the compound represented by the formula (10), to obtain a compound represented by the following formula (54): [ka] The compound represented by the formula was obtained in a yield of 56%.

[0205] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 16H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, which are derived from the photochromic compound, a peak of approximately 166.4H due to protons of the cyclohexane ring, butyl group, succinic acid moiety, dimethylsilyl group, and tetramethylene glycol group at around 0.0 to 3.0 ppm, and a 55H peak due to methoxy group, propyleneoxy group, ethyleneoxy group, and tetramethylene glycol group at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (54).

[0206] Example 19 The same procedure as in Example 17 was carried out except that in the third step, the compound of formula (46) was replaced by the compound of formula (41), to obtain a compound represented by the following formula (55): [ka] The compound represented by the formula:

[0207] 2nd process The same operation as in the fourth step of Example 17 was carried out to add succinic anhydride to the compound of formula (55) to obtain the compound of formula (56) below. [ka] The compound represented by the formula:

[0208] 3rd process The same procedure was carried out as in Example 17, except that the compound of formula (56) was used instead of the compound of formula (48) in the fifth step, to obtain a compound represented by the following formula (57): [ka] The compound represented by the formula was obtained in a yield of 54%.

[0209] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, the photochromic compound exhibited a 17H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, as well as peaks of approximately 194.9H due to protons of the cyclohexane ring, butyl group, succinic acid moiety, propyleneoxy group, and dimethylsiloxane group at around 0.0 to 3.0 ppm, and peaks of approximately 104.3H due to methoxy group, propyleneoxy group, ethyleneoxy group, and morpholino group at around δ 3.0 to 5.5 ppm, confirming that the structure matched the formula (57).

[0210] Example 20 1st step The reaction was carried out in the same manner as in the third step of Example 17, except that the compound of formula (7) was used instead of the compound of formula (45), to obtain a compound represented by the following formula (58): [ka] The compound represented by the formula:

[0211] 2nd process The same operation as in the fourth step of Example 17 was carried out to add succinic anhydride to the compound of formula (58) to obtain the compound of formula (59) [ka] The compound represented by the formula:

[0212] 3rd process The reaction was carried out in the same manner as in the fifth step of Example 1, except that the compound of formula (59) was used instead of the compound of formula (10), to obtain a compound represented by the following formula (60): [ka] The compound represented by the formula was obtained in a yield of 57%.

[0213] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 21H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, which are derived from the photochromic compound, a peak of approximately 67.6H due to the cyclohexane ring, methyl group, succinic acid moiety, and tetramethylene glycol protons at around 1.0 to 3.0 ppm, and a peak of approximately 123H due to the methoxy group, tetramethylene glycol group, and ethyleneoxy at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (60).

[0214] Example 21 1st step The same procedure was carried out as in Example 1, except that polypropylene glycol monobutyl ether having a number average molecular weight of 2500 was used instead of polyethylene glycol monomethyl ether having a number average molecular weight of 750 in the first step, to obtain a compound represented by the following formula (61): [ka] The compound represented by the formula:

[0215] 2nd process The same procedure was carried out as in Example 12, except that polyethylene glycol having a number average molecular weight of 1,000 was used instead of the compound of formula (40) in the first step, to obtain a compound represented by the following formula (62): [ka] The compound represented by the formula:

[0216] 3rd process The reaction was carried out in the same manner as in the second step of Example 1, except that the compound of formula (61) was used instead of the compound of formula (7) and the compound of formula (62) was used instead of the compound of formula (8), to obtain a compound represented by the following formula (63): [ka] The compound represented by the formula:

[0217] 4th step The same operation as in the fourth step of Example 17 was carried out to add succinic anhydride to the compound of formula (63) to obtain the compound of formula (64) below. [ka] The compound represented by the formula:

[0218] 5th step The reaction was carried out in the same manner as in the fifth step of Example 1, except that the compound of formula (64) was used instead of the compound of formula (10), to obtain a compound represented by the following formula (65): [ka] The compound represented by the formula was obtained in a yield of 63%.

[0219] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 21H peak due to aromatic protons and alkene protons at around δ 5.6 to 9.0 ppm, which are derived from the photochromic compound, a peak of approximately 160.2H due to protons of the cyclohexane ring, methyl group, succinic acid moiety, and butyl group at around 1.0 to 3.0 ppm, and a peak of approximately 231.2H due to methoxy group, ethylene glycol moiety, propylene glycol moiety, ethyleneoxy group, and butoxy group at around δ 3.0 to 5.5 ppm, confirming that the structure was consistent with the formula (65).

[0220] <Examples 22 to 25> The photochromic cured product was evaluated in the same manner as in Example 6. The results are shown in Table 3.

[0221] [Table 3]

[0222] <Examples 26 to 28 and Comparative Examples 5 to 7> (Fabrication and Evaluation of Photochromic Laminates) A photochromic curable composition was prepared by mixing the components according to the following formulation. The amounts of each component added are shown below. (Composition of polymerizable compounds) Polyethylene glycol dimethacrylate (average molecular weight 736) 32 parts by weight. Polyethylene glycol dimethacrylate (average molecular weight 536) 18 parts by weight. Trimethylolpropane trimethacrylate 37 parts by weight γ-methacryloyloxypropyltrimethoxysilane 2 parts by mass Glycidyl methacrylate 1 part by mass 0.3 parts by mass of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name: Irgacure 819, manufactured by BASF) (polymerization initiator). Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508) (stabilizer) 3 parts by mass. Ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (Irganox 245, manufactured by Ciba Specialty Chemicals) (stabilizer) 1 part by mass Manufactured by Toray Dow Corning Co., Ltd. Product name: L7001 (leveling agent) 0.1 parts by mass.

[0223] The photochromic curable composition was prepared by adding 2.5 mmol of photochromic compound per 100 g of polymerizable compound in the above-mentioned formulation. The photochromic curable composition thus obtained was used to obtain a photochromic laminate by a coating method. The polymerization method was as follows. First, a thiourethane-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. This thiourethane-based plastic lens was previously subjected to alkaline etching using a 10% aqueous sodium hydroxide solution at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0224] Using a spin coater (1H-DX2, manufactured by MIKASA), the surface of the plastic lens was coated with a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) at a rotation speed adjusted to a film thickness of 7 μm. Approximately 2 g of the photochromic composition obtained above was then spin coated at a rotation speed of 100 rpm for 25 seconds, followed by 1000 rpm for 10 to 20 seconds, to form a photochromic coating layer with a film thickness of 40 μm. The lens with the coating applied to its surface was placed in a nitrogen gas atmosphere with an output of 200mW / cm 2 The coating was cured by irradiating it with light for 90 seconds using a metal halide lamp, and then heated at 110°C for an additional hour to prepare a photochromic laminate having a photochromic layer. The obtained photochromic laminate was evaluated in the same manner as in Example 6. The evaluation results are shown in Table 4.

[0225] [Table 4] < / z> < / pc>

Claims

1. A photochromic compound represented by the following formula (1) or (2): 【Chemistry 1】 【Chemistry 2】 (In the formula, PC is a group having at least one photochromic moiety; In the case of the photochromic compound represented by the formula (1), a combination in which X1 is a polyoxypropylene group having 3 to 200 repeating units and X2 is a polyoxyethylene group having 3 to 200 repeating units; a combination of X1 being a polyoxyethylene group having 3 to 200 repeating units and X2 being a polyoxypropylene group having 3 to 200 repeating units; a combination of X1 being a polyoxytetramethylene group having 3 to 200 repeating units and X2 being any one of a polyoxyethylene group having 3 to 200 repeating units, a polyoxypropylene group having 3 to 200 repeating units, and a polysiloxane group having 3 to 200 repeating units and having a linear alkyl group having 1 to 10 carbon atoms as a substituent; X1 is a polysiloxane group having 3 to 200 repeating units and having a linear alkyl group having 1 to 10 carbon atoms as a substituent, and X2 is a combination of a polyoxyethylene group having 3 to 200 repeating units or a polyoxypropylene group having 3 to 200 repeating units, In the case of the photochromic compound represented by the formula (2), a combination of X1 being a polyoxypropylene group having 3 to 200 repeating units, X2 being a linear alkylene group having 12 to 30 carbon atoms, and X3 being a polyoxyethylene group having 3 to 200 repeating units; Z is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms; L1 is a divalent bond and a group selected from the following formulas: 【Transformation 3】 (In the formula, the dashed line represents the portion that binds to the photochromic moieties PC and X1.) L2 is an (m+1)-valent bond; L3 is a l+1-valent bond; When m and l are 1, L2 and L3 are groups selected from the following formulae: 【Chemistry 4】 (In the formula, the dashed line represents a bond to X1, X2, or X3.) When m and l are 2 or more, L2 and L3 are groups selected from the following formulae: 【Transformation 5】 (In the formula, the dashed line represents a bond to X1, X2, or X3.) n is an integer from 1 to 8, m is an integer from 1 to 4, and l is an integer from 1 to 4.

2. 2. The photochromic compound according to claim 1, wherein the photochromic moiety has at least one structure selected from the group consisting of naphthopyran, spirooxazine, spiropyran, fulgide, fulgimide, and diarylethene.

3. 3. The photochromic compound according to claim 2, wherein the naphthopyran moiety is an indenonaphthopyran moiety.

4. The indenonaphthopyran moiety is represented by the following formula (6): 【Transformation 6】 (In the formula, R １ and R ２ each independently represents a bond bonded to L1, a hydroxyl group, an alkyl group, a haloalkyl group, an optionally substituted cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, an amido group, a substituted amido group, an optionally substituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group, an optionally substituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an optionally substituted aralkyl group, an optionally substituted aralkoxy group, an optionally substituted aryloxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or an optionally substituted cycloalkylthio group; a is an integer from 0 to 4, and b is an integer from 0 to 4; When a is 2 to 4, a plurality of R ２ may be the same or different from each other, When b is 2 to 4, multiple R １ may be the same or different from each other, a is 2 to 4, and adjacent R ２ If there is a ２ Together they ２ may form a ring together with the carbon atom bonded to it which may contain an oxygen atom, a carbon atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent; b is 2 to 4, and adjacent R １ If there is a １ Together they １ may form a ring together with the carbon atom bonded to it which may contain an oxygen atom, a carbon atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent; R ３ and R ４ each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and the substituent may be bonded to L1; R ５ and R ６ each independently represents a bond bonded to L1, a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; R ５ and R ６ may combine together with the carbon atom at position 13 to which they are bonded to form an aliphatic ring having 3 to 20 ring carbon atoms, a condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the aliphatic ring, a heterocycle having 3 to 20 ring atoms, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle, provided that these rings may have a substituent; R １ , R ２ , R ３ The substituent of the aryl group of R ３ The substituents of the heteroaryl group of R ４ Substituents of the aryl group, substituents of the heteroaryl group, R ５ , and R ６ The n groups selected from the group consisting of are bonded to L1. The photochromic compound according to claim 3, represented by:

5. A photochromic curable composition comprising the photochromic compound according to any one of claims 1 to 4 and a polymerizable compound.

6. A cured product which is a polymer of the photochromic curable composition according to claim 5.

7. A lens comprising the cured product according to claim 6.

8. Eyeglasses comprising a lens according to claim 7.

Images